JP3187504B2 - Polyamide resin and its resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heat-meltable aromatic polyamide having high heat resistance. Further, the present invention relates to a novel aromatic polyamide resin composition having excellent dimensional stability and mechanical properties and also having excellent moldability.

[0002]

2. Description of the Related Art Conventionally, aromatic polyamides obtained by reacting an aromatic diamine or an aromatic diisocyanate with an aromatic dicarboxylic acid or a derivative thereof have been known for their excellent physical properties and good heat resistance. It is expected to be widely used in fields requiring heat resistance in the future. However, conventionally developed aromatic polyamides are:
Although there are many that have excellent mechanical properties and heat resistance,
All had the drawbacks of poor moldability and high water absorption.

For example, the following formula (Formula 8)

[0004]

Embedded image An aromatic polyamide having a basic skeleton represented by the following formula (a product of DuPont: trade name Kevlar) has excellent properties such as flame retardancy, heat resistance, high tension and high elastic modulus.
However, this aromatic polyamide does not have a clear glass transition temperature, has a thermal decomposition temperature of 430 ° C., and is close to the processing temperature and the thermal decomposition temperature, so that it is difficult to process as a molding material. was there. Therefore, it is only used in the field of fibers by wet spinning or pulp. In addition, the water absorption is as high as 4.5%,
Dimensional stability, insulation,
It is known that it adversely affects solder heat resistance and the like. ("Latest heat-resistant polymer": Sogo Gijutsu Center)

[0005]

An object of the present invention is to provide an aromatic polyamide having excellent processability and low water absorption, in addition to the excellent heat resistance inherent to the aromatic polyamide, and a process for producing the same. . It is still another object of the present invention to provide a novel resin composition which improves the mechanical strength and dimensional stability of the aromatic polyamide and further has excellent processability.

[0006]

Means for Solving the Problems The present inventors have found, after intensive investigations to achieve the above-mentioned problems, found a novel aromatic polyamide and the resin composition having the desired performance, the present invention described below Was completed.

[1] A structural unit represented by the following formula (I)
And an aromatic polyamide comprising only a group that blocks the terminal of the structural unit .

Embedded image (Wherein X is a halogen group, Z is a condensed polycyclic aromatic group or

Embedded image At least one group selected from the group consisting of Where Y is a direct bond,

Embedded image R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. The aromatic polyamide represented by). [2] The following formula (II)

Embedded image 1,3-bis (4-aminophenoxy) -5 represented by
-Halogenobenzene and / or 1,3-bis (3-
(Aminophenoxy) -5-halogenobenzene and an aromatic dicarboxylic acid dihalide in the presence of a dehydrohalogenating agent in an organic solvent at a reaction temperature of 60 ° C. or lower, which is obtained by polycondensation. [1] A method for producing an aromatic polyamide according to [1]. [3] Formula (II)

Embedded image 1,3-bis (4-aminophenoxy) -5 represented by
-Halogenobenzene and / or 1,3-bis (3-
Aminophenoxy) -5-halogenobenzene and an aromatic dicarboxylic acid in an organic solvent in the presence of a condensing agent in an organic solvent.
The method for producing an aromatic polyamide according to [1], wherein the aromatic polyamide is obtained by polycondensation at a reaction temperature of 150 ° C. [4] Formula (II)

Embedded image 1,3-bis (4-aminophenoxy) -5 represented by
-Halogenobenzene and / or 1,3-bis (3-
Aminophenoxy) -5-halogenobenzene and an aromatic dicarboxylic acid dialkylate and / or an aromatic dicarboxylic acid diallylate in an organic solvent for 100 to 30.
The method for producing an aromatic polyamide according to [1], wherein the aromatic polyamide is obtained by polycondensation at a reaction temperature of 0 ° C. [5] A structural unit represented by the following formula (I) and the structural unit
Consisting only of a group that blocks the terminal of the
Is a monovalent carboxylic acid, the carboxylic acid derivative or the monovalent carboxylic acid.
Aromatic polyamide sealed with amine .

Embedded image (Wherein X is a halogen group, Z is a condensed polycyclic aromatic group or

Embedded image At least one group selected from the group consisting of Where Y is a direct bond,

Embedded image R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. The aromatic polyamide represented by). [6] The method for producing an aromatic polyamide according to [5], wherein the polycondensation reaction is performed in the presence of a monovalent carboxylic acid or a carboxylic acid derivative, and the aromatic polycarboxylic acid or the aromatic dicarboxylic acid derivative is reacted. The amount is 0.7 to 1.0 mole per mole of aromatic diamine, and the amount of monovalent carboxylic acid or carboxylic acid derivative is 0.001 to 1.0 mole per mole of aromatic diamine. A process for producing an aromatic polyamide. [7] The method for producing an aromatic polyamide according to [5], wherein the polycondensation reaction is performed in the presence of a monovalent amine,
The amount of the aromatic diamine is 0.7 to 1.0 mol per 1 mol of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative, and the amount of the monovalent amine is the aromatic dicarboxylic acid or the aromatic dicarboxylic acid. 0.0 per mole of derivative
A method for producing an aromatic polyamide, characterized in that the reaction is carried out at a rate of from 01 to 1.0 mol. [8] The aromatic polyamide 10 according to [1] or [5].
An aromatic polyamide resin composition comprising 0 parts by weight and 5 to 100 parts by weight of a fibrous reinforcing material. [9] The aromatic polyamide resin composition according to [8], wherein the fibrous reinforcing material is selected from the group consisting of glass fibers, carbon fibers, potassium titanate fibers, and aromatic polyamide fibers. [10] The aromatic polyamide fiber is at least one selected from the group consisting of those having a repeating structural unit represented by the following formulas (1), (2) and (3), [9] The aromatic polyamide resin composition according to the above.

Embedded image

Embedded image

Embedded image [11] A molded article comprising the aromatic polyamide resin composition according to any one of [8] to [10].

[0008]

[0009]

[0010]

[0011]

[0012]

[0013]

[0014]

The aromatic polyamide of the present invention comprises a diamine component.
Formula (II)

Embedded image , Ie, 1,3-bis (4-aminophenoxy) -5-halogenobenzene and / or 1,3-bis (3-aminophenoxy) -5-halogenobenzene, and an aromatic dicarboxylic acid It is obtained by polymerizing an acid or a derivative thereof. Further, the aromatic polyamide resin composition of the present invention can be obtained by adding a fibrous reinforcing material to the aromatic polyamide of the present invention. That is,
The aromatic polyamide of the present invention and a resin composition thereof,
An aromatic polyamide characterized by using 1,3-bis (4-aminophenoxy) -5-halogenobenzene and / or 1,3-bis (3-aminophenoxy) -5-halogenobenzene as a diamine component. A thermoplastic aromatic polyamide and a resin composition having excellent processability in addition to the heat resistance of the above. Since the aromatic polyamide and its resin composition are thermoplastic in addition to excellent heat resistance, extrusion molding and injection molding are possible, and as a base material for space and aircraft, and a base material for electric and electronic parts, Furthermore, it can be expected to be used for multipurpose applications as a raw material for high-strength, high heat-resistant fibers by a melt spinning method, and is extremely useful.

[0016]

[0017]

The method for producing the aromatic polyamide of the present invention is not particularly limited, and various methods can be employed. For example,
A method according to claims 2-4 . The aromatic diamine used in this method is 1,3-bis (4-aminophenoxy) -5-halogenobenzene and / or 1,3-bis (4-aminophenoxy) -5-halogenobenzene.
Bis (3-aminophenoxy) -5-halogenobenzene. The aromatic dicarboxylic acids used in the method of claim 3 are aromatic dicarboxylic acids. For example, when a in the above formula is 0, phthalic acid, methylphthalic acid, ethylphthalic acid, methoxyphthalic acid, ethoxyphthalic acid, chlorophthalic acid, bromophthalic acid, isophthalic acid, methylisophthalic acid, ethylisophthalic acid, methoxyisophthalic acid, Examples include ethoxyisophthalic acids, chloroisophthalic acids, bromoisophthalic acids, terephthalic acid, methylterephthalic acids, ethylterephthalic acids, methoxyterephthalic acids, ethoxyterephthalic acids, chloroterephthalic acids, and bromoterephthalic acids. When a is 1 or 2, 2,2′-biphenyldicarboxylic acid, 4,4 ′
-Biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfide dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid,
4,4'-diphenylsulfonedicarboxylic acid, 4,4 '
-Diphenylmethanedicarboxylic acid, 2,2-bis (4-
Carboxyphenyl) propane and 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane. Further, when Z in the above formula is a condensed polycyclic aromatic group, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid,
6-naphthalenedicarboxylic acid and the like. These aromatic dicarboxylic acids are used alone or in combination of two or more.

In the method according to the second aspect, an aromatic dicarboxylic acid dihalide is used. For example, dihalides of the above-mentioned aromatic dicarboxylic acids, that is, aromatic dicarboxylic acid dichloride, aromatic dicarboxylic acid dibromide and the like can be mentioned. These aromatic dicarboxylic dihalides are:
They may be used alone or in combination of two or more.

Further, in the method of claim 4, an aromatic dicarboxylic acid dialkyl ester and / or an aromatic dicarboxylic acid diallyl ester are used. For example, each of the aromatic dicarboxylic acids has 1 to 10 carbon atoms such as dialkyl ester, diphenyl ester, di (fluorophenyl) ester, di (chlorophenyl) ester, di (bromophenyl) ester, di (methylphenyl) ester, Di (ethylphenyl) ester, di (propylphenyl) ester, di (isopropylphenyl) ester, di (butylphenyl) ester, di (isobutylphenyl) ester, di (t-butylphenyl) ester, di (methoxyphenyl) ester And di (ethoxyphenyl) ester, di (nitrophenyl) ester, di (phenylphenyl) ester, and dinaphthyl ester. These aromatic dicarboxylic diesters are used alone or in combination of two or more.

The above diamine component and aromatic dicarboxylic acid or a derivative thereof are polymerized in a solvent. As the solvent used, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3- Dimethyl-
2-imidazolidinone, N-methylcaprolactam, dimethylsulfoxide, dimethylsulfone, sulfolane,
Tetramethylurea, hexamethylphosphoramide, pyridine, α-picoline, β-picoline, γ-picoline,
2,4-lutidine, 2,6-lutidine, quinoline, isoquinoline, triethylamine, tripropylamine, tributylamine, tribunylamine, N, N-dimethylaniline, N, N-diethylaniline, dichloromethane, chloroform, carbon tetrachloride 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, 1,1,2,2-tetrachloroethane, tetrachloroethylene, n-hexane, cyclohexane, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, Acetonitrile, propionitrile, acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, isopropyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxy 1,4-dioxane, anisole, phenetole, benzyl ether, phenyl ether, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, benzene, toluene , O-xylene, m-
Xylene, p-xylene, diphenyl, terphenyl,
Benzyl chloride, nitrobenzene, 2-nitrotoluene,
3-nitrotoluene, 4-nitrotoluene, chlorobenzene, 2-chlorotoluene, 3-chlorotoluene, 4-
Chlorotoluene, o-dichlorobenzene, p-dichlorobenzene, bromobenzene, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2, 6-xylenol, 3,4-xylenol,
3,5-xylenol, o-chlorophenol, p-chlorophenol, methanol, ethanol, propanol, isopropanol, butanol, isobutanol,
t-butanol, cyclohexanol, benzyl alcohol, water and the like. These solvents may be used alone or in combination of two or more, depending on the type of the reaction raw material monomer and the polymerization technique.

When an aromatic dicarboxylic acid dihalide is used as a reaction raw material monomer, a dehydrohalogenating agent is usually used in combination. As the dehydrohalogenating agent used, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine,
N, N-dimethylbenzylamine, N, N-diethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-
Dimethylaniline, N, N-diethylaniline, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-methylmorpholine, N-ethylmorpholine, pyridine, α-picoline,
β-picoline, γ-picoline, 2,4-lutidine, 2,
6-lutidine, quinoline, isoquinoline, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate,
Calcium carbonate, sodium bicarbonate, potassium bicarbonate, calcium oxide, lithium oxide, sodium acetate,
Potassium acetate, ethylene oxide, propylene oxide and the like can be mentioned.

When an aromatic dicarboxylic acid is used as a reaction raw material monomer, a condensing agent is usually used.
As the condensing agent used, sulfuric anhydride, thionyl chloride,
Sulfite, picryl chloride, phosphorus pentoxide, phosphorus oxychloride, phosphite-pyridine condensing agent, triphenylphosphine-hexachloroethane condensing agent, propyl phosphoric anhydride-N-methyl-2-pyrrolidone condensing agent And the like. The reaction temperature varies depending on the polymerization technique and the type of solvent, but is usually 300 ° C. or lower. The reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure. The reaction time varies depending on the type of the reaction raw material monomer, the polymerization method, the type of the solvent, the type of the dehydrohalogenating agent, the type of the condensing agent and the reaction temperature, but usually, the aromatic polyamide represented by the formula (I) Usually, 10 minutes to 24 hours are sufficient to allow the reaction to proceed for a time sufficient to complete the production. By such a reaction, an aromatic polyamide having a repeating unit represented by the formula (I) is obtained.

That is, the aromatic polyamide of the present invention can be obtained by any method such as a low-temperature solution polycondensation method and a direct polycondensation method which are conventionally known as a method for synthesizing an aromatic polyamide.

The aromatic polyamide of the present invention has 1,3-bis (4-aminophenoxy) -5-halogenobenzene and / or 1,3-bis (4-aminophenoxy) -5
It is characterized by using bis (3-aminophenoxy) -5-halogenobenzene and an aromatic dicarboxylic acid derivative such as aromatic dicarboxylic acid or dicarboxylic acid dihalide. However, in order to improve the thermal stability and moldability of the aromatic polyamide, even if the terminal of the polymer molecule is blocked with a monovalent carboxylic acid or a carboxylic acid derivative or a monovalent amine, the aromatic polyamide is not modified. No problem. Such aromatic polyamides are
1,3-bis (4-aminophenoxy) of the above (II)
-5-halogenobenzene and / or 1,3-bis (3-aminophenoxy) -5-halogenobenzene as a main component is obtained by converting an aromatic diamine and an aromatic dicarboxylic acid or an aromatic dicarboxylic acid derivative into a monovalent carboxylic acid. Alternatively, it can be obtained by reacting in the presence of a carboxylic acid derivative or a monovalent amine. That is, a part of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative is a monocarboxylic acid derivative such as an aromatic and / or aliphatic and / or alicyclic monocarboxylic acid or a monocarboxylic acid halide, and a diamine component. It is prepared by replacing a part with an aromatic and / or aliphatic and / or alicyclic monoamine. Monocarboxylic acids used in these methods include benzoic acid, chlorobenzoic acids, bromobenzoic acids, methylbenzoic acids, ethylbenzoic acids, methoxybenzoic acids, ethoxybenzoic acids, nitrobenzoic acids, acetylbenzoic acids, acetoxybenzoic acid Acids, hydroxybenzoic acids, biphenylcarboxylic acids, benzophenonecarboxylic acids, diphenylethercarboxylic acids, diphenylsulfidecarboxylic acids, diphenylsulfonecarboxylic acids, 2,2-diphenylpropanecarboxylic acids, 2,2-diphenyl-1,1,1,3 , 3,
3-hexafluoropropanecarboxylic acids, naphthalenecarboxylic acids, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, nitroacetic acid, propionic acid, butyric acid, valeric acid,
Examples include caproic acid and cyclohexanecarboxylic acid. Monocarboxylic acids may be used alone or in combination of two or more.

Further, as the monocarboxylic acid halide,
For example, there may be mentioned the acid chlorides and acid bromides of the aforementioned monocarboxylic acids. These monocarboxylic acid halides may be used alone or in combination of two or more.

The monocarboxylic acid esters include:
For example, alkyl esters of the above-mentioned monocarboxylic acids having 1 to 10 carbon atoms, phenyl esters, fluorophenyl esters, chlorophenyl esters, bromophenyl esters, methylphenyl esters, ethylphenyl esters, propylphenyl esters, isopropylphenyl esters, butylphenyl esters , Isobutylphenyl ester, t-butylphenyl ester, methoxyphenyl ester, ethoxyphenyl ester, nitrophenyl ester, phenylphenyl ester, naphthyl ester and the like. These monocarboxylic acid esters are used alone or in combination of two or more.

The amount of the monocarboxylic acid used is from 0.001 to 1.0 mol per mol of the aromatic diamine.
If the amount is less than 0.001 mol, the viscosity increases during high-temperature molding, which causes a reduction in moldability. On the other hand, if it exceeds 1.0 mol, the mechanical properties deteriorate. The preferred amount is
The ratio is 0.01 to 0.5 mol.

When a monovalent amine is used, for example, aniline, o-toluidine, m-toluidine, p-toluidine,
-Toluidine, 2,3-xylidine, 2,4-xylidine, 5,5-xylidine, 2,6-xylidine, 3,4-
Xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p- Nitroaniline, o-anisidine, m-anisidine, p-
Anisidine, o-phenetidine, m-phenetidine, p
-Phenetidine, o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminobiphenyl
Aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminobenzophenone
Aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfide
Aminophenylphenylsulfone, 4-aminophenylphenylsulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2-amino-1
-Naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7
-Amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, methylamine, dimethylamine, ethylamine, diethylamine, propylamine , Dipropylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, isobutylamine, diisobutylamine, pentylamine, dipentylamine, benzylamine, cyclopropylamine, cyclobutylamine,
Cyclopentylamine, cyclohexylamine and the like can be mentioned. These monoamines are used alone or in combination of two or more. The amount of the monoamine used is 0.001 to 1.0 mol per 1 mol of aromatic dicarboxylic acids. If the amount is less than 0.001 mol, the viscosity increases during high-temperature molding, which causes a reduction in moldability. Also, 1.0
If the molar ratio is exceeded, the mechanical properties deteriorate. A preferred amount is 0.01 to 0.5 mol.

The aromatic polyamide and the resin composition of the present invention can be subjected to melt molding. In this case, other thermoplastic resins can be blended in an appropriate amount according to the purpose within a range that does not impair the purpose of the present invention. As thermoplastic resins that can be blended, polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polyimide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyphenylenesulfide, polyamideimide, polyetherimide, modified And polyphenylene oxide. It is also possible to add a thermosetting resin or a filler to such an extent that the object of the present invention is not impaired. Examples of the thermosetting resin include a phenol resin and an epoxy resin. Fillers include graphite, carborundum, silica stone powder, molybdenum disulfide,
Reinforcement materials such as abrasion resistance improving materials such as fluororesins, glass fibers, carbon fibers, boron fibers, silicon carbide fibers, carbon whiskers, asbestos, metal fibers, ceramic fibers, etc., and difficulties in antimony trioxide, magnesium carbonate, calcium carbonate, etc. Flame retardant, electrical properties improver such as clay and mica, tracking improver such as asbestos, silica, graphite, acid resistant improver such as barium sulfate, silica, calcium metasilicate, iron powder, zinc powder, aluminum Thermal conductivity improving materials such as powder and copper powder, and other glass beads, talc, diatomaceous earth, alumina, shirasubarun, hydrated alumina, metal oxides, coloring agents, and the like.

As the fibrous reinforcing material used in the present invention, various materials are used, for example, glass fiber, carbon fiber,
Usually known inorganic or organic fibers such as potassium titanate fiber, aromatic polyamide fiber, silicon carbide fiber, alumina fiber, boron fiber, and ceramic fiber can be used, but particularly preferably used are glass fiber, carbon fiber, and titanium fiber. Potassium acid fiber and aromatic polyamide fiber.

The glass fiber used in the present invention is obtained by quenching molten glass while stretching it by various methods to form a thin fiber having a predetermined diameter. A strand in which single fibers are bundled with a sizing agent, It means roving or the like in which strands are uniformly arranged in a bundle, and any of them can be used in the present invention. The glass fiber may be treated with a silane coupling agent such as aminosilane or epoxysilane, chromic chloride, or a surface treatment agent according to the intended purpose in order to have an affinity with the base resin of the present invention. it can. The length of the glass fiber in the present invention greatly affects the physical properties of the obtained molded article and the workability during the production of the molded article. Generally, as the glass fiber length increases, the physical properties of the molded article improve, but conversely, the workability during the production of the molded article deteriorates. For this reason, in the present invention, the length of the glass fiber is preferably in the range of 0.1 to 6 mm, more preferably 0.3 to 4 mm, because the physical properties and workability of the molded product are well balanced.

The carbon fiber used in the present invention is a high elasticity and high strength fiber obtained by carbonizing polyacrylonitrile, petroleum pitch or the like as a main raw material. In the present invention, both polyacrylonitrile and petroleum pitch can be used. Carbon fibers having an appropriate diameter and an appropriate aspect ratio (length / diameter ratio) are used depending on the reinforcing effect and the mixing property. The diameter of the carbon fiber is usually 5 to 20 μm,
Particularly, those having a thickness of about 8 to 15 μm are preferable. In addition, the aspect ratio is 1 to 600, in particular, the reinforcing effect and the mixing property,
About 100 to 350 is preferable. If the aspect ratio is small, there is no reinforcing effect, and if the aspect ratio is large, the mixing property is poor, and a good molded product cannot be obtained. In addition, those obtained by treating the surface of the carbon fiber with various treatment agents, for example, an epoxy resin, a polyamide resin, a polycarbonate resin, a polyacetal resin, and the like, and those using a known surface treatment agent depending on the purpose are also used.

The potassium titanate fiber used in the present invention is a kind of high-strength fiber (whisker), and its basic chemical composition is K ₂ O.6TiO ₂ , K ₂ O.6TiO ₂ .1 / 2H ₂ O. Having a typical melting point of 1300 to 1350
° C. An average fiber length of 5 to 50 μm and an average fiber diameter of 0.05 to 1.0 μm are applied, but an average fiber length of 20 to 30 μm and an average fiber diameter of 0.1 to 0.3 μm
Are preferred. The potassium titanate fiber can be usually used without any treatment, but in order to have an affinity with the base resin of the present invention, a silane coupling agent such as aminosilane or epoxysilane, chromic chloride, or other surface treatment according to the purpose. Agents can be used.

The aromatic polyamide fiber used in the present invention is a relatively newly developed heat-resistant organic fiber,
It is expected to expand into various fields by utilizing many unique characteristics. For example, as typical examples, the structural formulas (1) (formula 17) and (2) (formula 1) having the following repeating units
8) and those represented by the formula (3) (Chemical Formula 19), and one or a mixture of two or more of these are used.

[0036]

Embedded image Example) DuPont trademark: Kevlar

[0037]

Embedded image Example) DuPont trademark: Nomex Teijin trademark: Conex

[0038]

Embedded image In the case of 5 parts by weight or less of the glass fiber and the carbon fiber, the reinforcing effect peculiar to the glass fiber or the carbon fiber characteristic of the present invention cannot be obtained. Conversely, if it is used in an amount of 100 parts by weight or more, the fluidity during molding of the composition becomes poor, and it becomes difficult to obtain a satisfactory molded product. If the content of the potassium titanate fiber is 5 parts by weight or less, the improvement in mechanical properties at high temperatures, which is a feature of the present invention, is insufficient. Conversely, if the amount is large, dispersion in melt mixing becomes insufficient, and further, the fluidity becomes low, and molding under ordinary conditions becomes difficult, which is not preferable. The preferred amount is 10 to 100 parts by weight. When the amount of the aromatic polyamide fiber is 5 parts by weight or less, a composition excellent in moldability and mechanical strength, which is a feature of the present invention, cannot be obtained. If it is used in an amount of 100 parts by weight or more, the fluidity of the composition at the time of molding deteriorates, and it becomes difficult to obtain a satisfactory molded product. The preferred amount is 10 to 50 parts by weight.

The resin composition using the aromatic polyamide of the present invention can be produced by a generally known method, but the following method is particularly preferable.

(1) Aromatic polyamide powder and fibrous reinforcing material are premixed using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill, ribbon blender, and the like, and then a conventionally known melt mixer, hot roll After kneading, the mixture is formed into pellets or powder.

(2) The aromatic polyamide powder is previously dissolved or suspended in an organic solvent, the fibrous reinforcing material is immersed in this solution or suspension, and then the solvent is removed in a hot air oven. Pellet or powder. In this case, as a solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-
2-imidazolidinone, N-methylcaprolactam,
1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy)
Ethane, bis {2- (2-methoxyethoxy) ethyl}
Ether, tetrahydrofuran, 1,3-dioxane,
Examples thereof include 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethyl urea, and hexamethyl phosphoramide. These organic solvents may be used alone or in combination of two or more.

The aromatic polyamide resin composition of the present invention comprises:
It is molded by a known molding method such as an injection molding method, an extrusion molding method, a compression molding method, and a rotational molding method, and put into practical use.

[0043]

EXAMPLES Hereinafter, the production examples of the aromatic polyamide of the present invention and the physical properties and performance of the obtained aromatic polyamide will be described in detail with reference to Examples and Comparative Examples.

In the examples, various physical properties were measured by the following methods. Logarithmic viscosity: Measured at 35 ° C. after dissolving 0.50 g of polyamide powder in 100 ml of hexamethylphosphoric triamide. Glass transition temperature (Tg): Measured by DSC (Shimadzu DT-40 series, DSC-41M). 5% weight loss temperature: DTA-TG (Shimadzu DT-
40 series, measured by DTG-40M). Melt viscosity: Measured with a load of 100 kg using a Shimadzu Koka type flow tester CFT500A.

Example 1 In a vessel equipped with a stirrer and a nitrogen inlet tube, under a nitrogen atmosphere, 32.68 g (0.10 mol) of 1,3-bis (4-aminophenoxy) -5-chlorobenzene and N-methyl- After charging and dissolving 410 g of 2-pyrrolidone, 24.29 g (0.24 mol) of triethylamine was added, and the mixture was cooled to 5 ° C. Thereafter, stirring was strengthened, and 20.30 g (0.10 mol) of terephthalic acid chloride was charged, and stirring was continued at room temperature for 3 hours. The viscous polymer solution thus obtained was discharged into vigorously stirred methanol to precipitate a white powder. This white powder was separated by filtration, washed with methanol, dried at 180 ° C. under reduced pressure for 12 hours, and dried.
4.00 g (yield 96.3%) of polyamide powder was obtained. The logarithmic viscosity of this polyamide powder is 0.81 dl /
g, glass transition temperature is 241 ° C, 5% weight loss temperature is 4
70 ° C. The results of elemental analysis of the obtained polyamide powder are as follows.

C H N calculated value (%) 68.35 3.75 6.13 actually measured value (%) 69.25 3.60 5.98 Also, the infrared absorption spectrum of the obtained polyamide powder is shown in FIG. Shown in the figure. This spectrum diagram, in the vicinity of 1650 cm ^-1 and 1520 cm ^-1 which is the characteristic absorption band of amide,
Significant absorption was observed. Furthermore, after dissolving the obtained polyamide powder in N-methyl-2-pyrrolidone, it was cast on a glass plate and heated at 150 ° C. for 1 hour and at 250 ° C. for 2 hours to obtain a colorless and transparent polyamide film. The tensile strength of this polyamide film is 1400 Kg / c
m ² and the tensile elongation were 25%. Both measurement methods are AS
According to TM D-882. The water absorption of this film was 0.71%. The measurement method is ASTM D-750.
According to -63.

Example 2 The procedure of Example 1 was repeated, except that terephthalic acid chloride was replaced with isophthalic acid chloride. 44.50 g of a polyamide powder having a logarithmic viscosity of 0.75 dl / g.
(Yield 97.4%). The glass transition temperature of this polyamide powder was 228 ° C., and the 5% weight loss temperature was 472 ° C. The results of elemental analysis of the obtained polyamide powder are as follows.

C H N calculated value (%) 68.35 3.75 6.13 actually measured value (%) 69.18 3.55 5.91 The infrared absorption spectrum of the obtained polyamide powder is shown in the second section. Shown in the figure. This spectrum diagram, in the vicinity of 1660 cm ^-1 and 1540 cm ^-1 which is the characteristic absorption band of amide,
Significant absorption was observed. Further, a colorless and transparent polyamide film was obtained in the same manner as in Example 1 using the obtained polyamide powder. The tensile strength of this polyamide film was 1280 kg / cm ² , the tensile elongation was 28%, and the water absorption was 0.68%.

Example 3 20.30 g of terephthalic acid chloride in Example 1
(0.10 mol) to 10.15 g of terephthalic acid chloride
(0.05 mol) and 10.15 g of isophthalic chloride
(0.05 mol) was carried out in the same manner as in Example 1, except that the logarithmic viscosity was 0.77 dl / g.
4.55 g (97.5% yield) was obtained. The glass transition temperature of this polyamide powder was 233 ° C, and the 5% weight loss temperature was 468 ° C. Using the obtained polyamide powder,
A colorless and transparent polyamide film was obtained in the same manner as in Example 1. The tensile strength of this polyamide film is 1310
Kg / cm ² , tensile elongation 28%, water absorption 0.69
%Met.

Example 4 Example 1 was repeated except that 1,3-bis (4-aminophenoxy) -5-chlorobenzene in Example 1 was replaced with 1,3-bis (3-aminophenoxy) -5-chlorobenzene. In the same manner, 44.55 g (yield 97.5%) of a polyamide powder having a logarithmic viscosity of 0.86 dl / g was obtained. The glass transition temperature of this polyamide powder was 197 ° C, and the 5% weight loss temperature was 467 ° C. The results of elemental analysis of the obtained polyamide powder are as follows.

C H N calculated value (%) 68.35 3.75 6.13 actually measured value (%) 69.00 3.55 6.03 Further , the infrared absorption spectrum of the obtained polyamide powder is shown in the third part. Shown in the figure. This spectrum diagram, in the vicinity of 1660 cm ^-1 and 1540 cm ^-1 which is the characteristic absorption band of amide,
Significant absorption was observed. Further, a colorless and transparent polyamide film was obtained in the same manner as in Example 1 using the obtained polyamide powder. The tensile strength of this polyamide film was 1160 kg / cm ² , the tensile elongation was 30%, and the water absorption was 0.78%.

Example 5 The procedure of Example 4 was repeated except that terephthalic acid chloride was replaced with isophthalic acid chloride. 44.78 g of a polyamide powder having a logarithmic viscosity of 0.77 dl / g was used.
(Yield 98.0%). The glass transition temperature of this polyamide powder was 194 ° C, and the 5% weight loss temperature was 460 ° C. The results of elemental analysis of the obtained polyamide powder are as follows.

C H N calculated value (%) 68.35 3.75 6.13 actually measured value (%) 69.11 3.61 5.99 The infrared absorption spectrum of the obtained polyamide powder is shown in FIG. Shown in the figure. This spectrum diagram, in the vicinity of 1650 cm ^-1 and 1520 cm ^-1 which is the characteristic absorption band of amide,
Significant absorption was observed. Further, a colorless and transparent polyamide film was obtained in the same manner as in Example 1 using the obtained polyamide powder. The tensile strength of this polyamide film was 1100 kg / cm ² , the tensile elongation was 36%, and the water absorption was 0.77%.

Example 6 20.30 g of terephthalic acid chloride in Example 4
(0.10 mol) to 10.15 g of terephthalic acid chloride
(0.05 mol) and 10.15 g of isophthalic chloride
(0.05 mol) was carried out in the same manner as in Example 4, and the logarithmic viscosity was 0.80 dl / g.
4.50 g (97.4% yield) were obtained. The glass transition temperature of this polyamide powder was 195 ° C, and the 5% weight loss temperature was 462 ° C. Using the obtained polyamide powder,
A colorless and transparent polyamide film was obtained in the same manner as in Example 1. The tensile strength of this polyamide film is 1120
Kg / cm ² , tensile elongation 35%, water absorption 0.77
%Met.

Example 7 In a vessel equipped with a stirrer and a nitrogen inlet tube, under a nitrogen atmosphere, 16.62 g (0.10 mol) of terephthalic acid, 20.0 g of lithium chloride, 60.0 g of calcium chloride, 200 g of pyridine, 200 g of phosphorus suboxide 62.0 g of triphenyl acid (0.
20 g) and 850 g of N-methyl-2-pyrrolidone were charged and dissolved, and then heated to 120 ° C. There, 1,
32.68 g (0.10 mol) of 3-bis (3-aminophenoxy) -5-chlorobenzene was charged and stirred at 120 ° C. for 2 hours. The viscous polymer solution thus obtained was discharged into vigorously stirred methanol to precipitate a white powder. This white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours.
g (yield 98.1%) of a polyamide powder was obtained. The logarithmic viscosity of this polyamide powder was 0.92 dl / g, the glass transition temperature was 197 ° C., and the 5% weight loss temperature was 465 ° C. The results of elemental analysis of the obtained polyamide powder are as follows.

C H N calculated value (%) 68.35 3.75 6.13 actually measured value (%) 69.15 3.58 5.88 The infrared absorption spectrum of the obtained polyamide powder is shown in FIG. Shown in the figure. The spectrogram is exactly the same as the polyamide powder obtained in Example 4, in the vicinity of 1650 cm ^-1 and 1540 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Example 8 19.42 g (0.10 mol) of dimethyl terephthalate, 1,3-bis (3-aminophenoxy) -5-chlorobenzene 32 in a vessel equipped with a stirrer and a nitrogen inlet tube under a nitrogen atmosphere. .68 g (0.10 mol) and 1000 g of diphenyl ether were charged and stirred at 250 ° C. for 8 hours. The reaction product thus obtained was discharged into vigorously stirred methanol to precipitate a white powder. This white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours to obtain 43.31 g (yield 94.8%) of a polyamide powder. The logarithmic viscosity of this polyamide powder was 0.78 dl / g, the glass transition temperature was 195 ° C, and the 5% weight loss temperature was 462 ° C. The results of elemental analysis of the obtained polyamide powder are as follows.

C H N calculated value (%) 68.35 3.75 6.13 actually measured value (%) 69.08 3.61 6.03 Further , the infrared absorption spectrum of the obtained polyamide powder is shown in FIG. Shown in the figure. The spectrogram is exactly the same as the polyamide powder obtained in Example 4, in the vicinity of 1640 cm ^-1 and 1520 cm ^-1 which is the characteristic absorption band of amide, significant absorption was observed.

Example 9 In a vessel equipped with a stirrer and a nitrogen inlet tube, under a nitrogen atmosphere, 32.68 g (0.10 mol) of 1,3-bis (3-aminophenoxy) -5-chlorobenzene and N-methyl- After charging and dissolving 410 g of 2-pyrrolidone, 24.29 g (0.24 mol) of triethylamine was added,
Cooled to 5 ° C. Thereafter, the stirring was strengthened and 19.29 g (0.095 mol) of terephthalic acid chloride was charged, and stirring was continued at room temperature for 2 hours. Then, benzoyl chloride 2.
11 g (0.015 mol) were charged and stirring was continued at room temperature for 2 hours. The resulting polymer solution was discharged into vigorously stirred methanol to precipitate a white powder. This white powder was separated by filtration, washed with methanol, and dried at 180 ° C for 1 hour.
After drying under reduced pressure for 2 hours, 43.82 g (yield 95.1%)
Was obtained. The logarithmic viscosity of this polyamide powder was 0.48 dl / g. The melt viscosity of the obtained polyamide powder was measured.
It was 00 poise. Further, the obtained strand was pale yellow, transparent, highly flexible, and very tough. Also,
The thermal stability of the polyamide obtained in this example was measured by changing the residence time in the cylinder of the flow tester. The measurement was performed at 300 ° C. The results are shown in FIG. Even if the residence time in the cylinder becomes longer, the melt viscosity hardly changes, indicating that the thermal stability is good. Also,
The heat distortion temperature of a molded product obtained by compression molding this polyamide powder at 280 ° C. and 150 kg / cm ² for 15 minutes was 185 ° C. The measurement method is ASTM D-
648, load 18.6 Kg / cm ² .

Example 10 31.04 g (0.095 mol) of 1,3-bis (3-aminophenoxy) -5-chlorobenzene and N-methyl- After charging and dissolving 410 g of 2-pyrrolidone, 24.29 g (0.24 mol) of triethylamine was added, and the mixture was cooled to 5 ° C. Thereafter, the stirring was increased and 20.30 g (0.10 mol) of terephthalic acid chloride was charged, and stirring was continued at room temperature for 2 hours. Then, 1.40 g of aniline
(0.015 mol) and stirring was continued at room temperature for 2 hours. The resulting polymer solution was discharged into vigorously stirred methanol to precipitate a white powder. This white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours to obtain 42.51 g (yield 94.5%) of a polyamide powder. The logarithmic viscosity of this polyamide powder was 0.46 dl / g. The melt viscosity of the obtained polyamide powder was measured.
Poise. Further, the obtained strand was pale yellow, transparent, highly flexible, and very tough.

Comparative Example 1 Under a nitrogen atmosphere, 2.16 g (0.020 mol) of p-phenylenediamine and 56.2 g of N-methyl-2-pyrrolidone were charged and dissolved in a vessel equipped with a stirrer and a nitrogen inlet tube. After that, 4.86 g of triethylamine (0.04
8 mol) and cooled to 5 ° C. Thereafter, the stirring was increased to 3.86 g (0.019 mol) of terephthalic acid chloride.
And the stirring was continued at room temperature for 2 hours. Thereafter, 0.443 g (0.003 mol) of benzoyl chloride was charged, and stirring was continued at room temperature for 2 hours. The resulting polymer solution was discharged into vigorously stirred methanol to precipitate a white powder. This white powder was separated by filtration, washed with methanol, and dried under reduced pressure at 180 ° C. for 12 hours.
g (yield 97.7%) of polyamide powder was obtained. When the glass transition temperature of this polyamide powder was measured, no clear value was shown. The melt viscosity was measured at 300 ° C. and 400 ° C., but no melt flow occurred at any temperature.

Comparative Example 2 A polyamide powder was synthesized in the same manner as in Example 9 except that benzoyl chloride was not used. The logarithmic viscosity of the polyamide powder was 0.48 dl / g. When the residence time in the flow tester cylinder was changed and the melt viscosity was measured in the same manner as in Example 9, the melt viscosity increased as the residence time increased, as shown in FIG. The heat stability was inferior to the obtained polyamide.

Examples 11 and 12 The polyamides obtained in Examples 1 and 4
Silane-treated glass fiber having a fiber length of 3 mm and a fiber diameter of 13 μm with respect to parts by weight (Nitto Boseki Co., Ltd .: CS-3)
PE-476S) was added in the amount shown in Table 1, and mixed with a drum blender mixer (manufactured by Kawada Seisakusho).
After melt-kneading at a temperature of 300 ° C. using a 0 mm single screw extruder, the strand was air-cooled and cut to obtain a pellet. The obtained pellets were subjected to injection molding (Arburg molding machine, maximum clamping force 35 tons, injection pressure 500 kg / cm ² , cylinder temperature 300 ° C., mold temperature 150 ° C.) to obtain various test pieces for measurement. Was. Measured tensile strength (AS
TM D-638), flexural strength and flexural modulus (ASTM D-790), Izod impact strength (notched) (ASTM D-256), heat distortion temperature (AS
TM D-648), molding shrinkage (ASTM D-95)
Table 1 shows the results of 5).

[0064]

[Table 1]

Comparative Examples 3 and 4 The polyamides obtained in Examples 1 and 4
Table 2 shows the results obtained by using the same glass fibers as those in Examples 11 and 12 in parts by weight outside the scope of the present invention.

[0066]

[Table 2]

Examples 13 and 14 The polyamides obtained in Examples 1 and 4 respectively
Carbon fiber having an average diameter of 12 μm, a length of 3 mm, and an aspect ratio of 250 (trade name of Toray Co., Ltd.) was added to the parts by weight as shown in Table-3. Were obtained.

[0068]

[Table 3]

Comparative Examples 5 and 6 The polyamides obtained in Examples 1 and 4
120 parts by weight of the same carbon fibers as in Examples 13 and 14 were added to the parts by weight of Examples 13 and 14, respectively.
Extruded strands were tried in the same manner as in Example 1, but none of them could be made into strands.

Examples 15 and 16 The polyamides obtained in Examples 1 and 4
The cross-sectional diameter is 0.2 μm and the average fiber length is 20
μm potassium titanate fiber (Otsuka Chemical Co., Ltd .: Tismo D) was added in the amount shown in Table 4, and the results shown in Table 4 were obtained in the same manner as in Examples 11 and 12.

[0071]

[Table 4]

Examples 17 and 18 The polyamides obtained in Examples 1 and 4, respectively,
To the parts by weight, an aromatic polyamide having an average fiber length of 3 mm (Dupont: Kevlar) was added in the amount shown in Table 5, and the results shown in Table 5 were obtained in the same manner as in Examples 11 and 12. Was.

[0073]

[Table 5]

[0074]

The present invention provides a completely novel aromatic polyamide having excellent processability or heat stability in addition to the excellent heat resistance inherent to the aromatic polyamide. Furthermore, the aromatic polyamide resin composition of the present invention has excellent dimensional stability and mechanical strength, and has extremely good workability.
It is an extremely useful material used in electrical / electronic parts, automobile parts, precision machine parts, medical equipment parts, and base materials for spacecraft, etc., which require these physical properties. Big.

[Brief description of the drawings]

FIG. 1 is a diagram of an infrared absorption spectrum of a polyamide powder obtained in Example 1 according to the present invention.

FIG. 2 is a diagram of an infrared absorption spectrum of a polyamide powder obtained in Example 2 according to the present invention.

FIG. 3 is a diagram of an infrared absorption spectrum of a polyamide powder obtained in Example 4 according to the present invention.

FIG. 4 is a diagram of an infrared absorption spectrum of a polyamide powder obtained in Example 5 according to the present invention.

FIG. 5 is a diagram of an infrared absorption spectrum of a polyamide powder obtained in Example 7 according to the present invention.

FIG. 6 shows an infrared absorption spectrum of a polyamide powder obtained in Example 8 according to the present invention.

FIG. 7 shows a comparison between the thermal stability of each of the polyamide powders obtained in Example 9 and Comparative Example 2 according to the present invention. The resin residence time in the cylinder of the flow tester was measured at a measurement temperature of 300 ° C. and a load of 100 kg. It is the result of measuring the melt viscosity by changing, where A is that of Example 9 and B is that of Comparative Example 2.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd. (56) References JP-A-62-177020 (JP, A) JP-A-62 -1777023 (JP, A) JP-A-5-222188 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 69/00-69/50 C08K 3/00-13/08 C08L 77/00-77/12 CA (STN) REGISTRY (STN)

Claims (11)

(57) [Claims] 1. A structural unit represented by the following formula (I) :
An aromatic polyamide comprising only a group that blocks a terminal of the structural unit . Embedded image (Wherein X is a halogen group, Z is a condensed polycyclic aromatic group or the following formula: At least one group selected from the group consisting of Here, Y is a direct bond, and the following formula: R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. The aromatic polyamide represented by). 2. The following formula (II): 1,3-bis (4-aminophenoxy) -5 represented by
-Halogenobenzene and / or 1,3-bis (3-
(Aminophenoxy) -5-halogenobenzene and an aromatic dicarboxylic acid dihalide in the presence of a dehydrohalogenating agent in an organic solvent at a reaction temperature of 60 ° C. or lower, which is obtained by polycondensation. A method for producing the aromatic polyamide according to claim 1. 3. A compound of the formula (II) 1,3-bis (4-aminophenoxy) -5 represented by
-Halogenobenzene and / or 1,3-bis (3-
Aminophenoxy) -5-halogenobenzene and an aromatic dicarboxylic acid in an organic solvent in the presence of a condensing agent in an organic solvent.
The method for producing an aromatic polyamide according to claim 1, wherein the aromatic polyamide is obtained by polycondensation at a reaction temperature of 150 ° C. 4. A compound of the formula (II) 1,3-bis (4-aminophenoxy) -5 represented by
-Halogenobenzene and / or 1,3-bis (3-
Aminophenoxy) -5-halogenobenzene and an aromatic dicarboxylic acid dialkylate and / or an aromatic dicarboxylic acid diallylate in an organic solvent for 100 to 30.
The method for producing an aromatic polyamide according to claim 1, wherein the aromatic polyamide is obtained by polycondensation at a reaction temperature of 0 ° C. 5. A structural unit represented by the following formula (I) :
It consists only of a group that blocks the end of the structural unit,
Is terminated with a monovalent carboxylic acid, the carboxylic acid derivative or the like.
Or an aromatic polyamide sealed with a monovalent amine . Embedded image (Wherein X is a halogen group, Z is a condensed polycyclic aromatic group or the following formula: At least one group selected from the group consisting of Here, Y is a direct bond, and the following formula: R represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a halogen group, a phenyl group, a represents 0, 1 or 2, and b represents 0.
Or, represents an integer of 1 to 4. N represents an integer of 1 to 1000. The aromatic polyamide represented by). 6. The method for producing an aromatic polyamide according to claim 5, wherein the polycondensation reaction is carried out in the coexistence of a monovalent carboxylic acid or a carboxylic acid derivative, and the aromatic dicarboxylic acid or the aromatic dicarboxylic acid is used. The amount of the derivative is 0.7 to 1.0 mol per mol of the aromatic diamine, and the amount of the monovalent carboxylic acid or the carboxylic acid derivative is 0.001 to 1 mol per mol of the aromatic diamine. A method for producing an aromatic polyamide, wherein the reaction is carried out at a ratio of 0 mol. 7. The method for producing an aromatic polyamide according to claim 5, wherein the polycondensation reaction is carried out in the presence of a monovalent amine, and the amount of the aromatic diamine is aromatic dicarboxylic acid or aromatic dicarboxylic acid. 0.7-per mole of acid derivative
Aroma, characterized in that the reaction is carried out at a ratio of 0.001 to 1.0 mol with respect to 1 mol of the aromatic dicarboxylic acid or the aromatic dicarboxylic acid derivative. For producing aromatic polyamides. 8. An aromatic polyamide resin composition comprising 100 parts by weight of the aromatic polyamide according to claim 1 or 5 and 5 to 100 parts by weight of a fibrous reinforcing material. 9. The fibrous reinforcing material is glass fiber, carbon fiber,
9. The aromatic polyamide resin composition according to claim 8, which is selected from the group consisting of potassium titanate fibers and aromatic polyamide fibers. 10. The aromatic polyamide fiber is at least one selected from the group consisting of those having a repeating structural unit represented by the following formulas (1), (2) and (3). Item 10. An aromatic polyamide resin composition according to item 9. Embedded image Embedded image Embedded image 11. A molded article comprising the aromatic polyamide resin composition according to claim 8.